WO2024007759A1 - 一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用 - Google Patents

一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用 Download PDF

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WO2024007759A1
WO2024007759A1 PCT/CN2023/096216 CN2023096216W WO2024007759A1 WO 2024007759 A1 WO2024007759 A1 WO 2024007759A1 CN 2023096216 W CN2023096216 W CN 2023096216W WO 2024007759 A1 WO2024007759 A1 WO 2024007759A1
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nano
preparation
gelling agent
micro
acid
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French (fr)
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刘云峰
刘雨舟
马晨洮
唐永帆
张燕
张倩
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C08F226/04—Diallylamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes

Definitions

  • the invention relates to the technical field of oil and gas field development, and specifically relates to a micro-nano-scale spherical modified silicic acid liquid gelling agent and its preparation method and application.
  • Acid fracturing is the most important production stimulation measure among oil and gas field production stimulation technologies. It usually uses acid to dissolve or etch the target formation to form oil and gas flow channels, thereby achieving the purpose of increasing production.
  • the main influencing factors of acid fracturing operations are the conductivity of fractures and the length of dissolution fractures. Reducing the dissolution rate of acid solution is one of the important factors to ensure the quality of acidizing operations.
  • increasing the viscosity of acid solution is generally used to reduce the corrosion rate of acid solution. This is because the molecular chain network structure can reduce the diffusion rate of hydrogen ions, thereby reducing the corrosion efficiency of acid solution on rock surfaces. Therefore, the research on acid gelling agents has become one of the important topics in the field of oil and gas field development.
  • CN113563505A discloses a temperature-resistant, acid-resistant and salt-resistant acid liquid gelling agent and a preparation method thereof.
  • the acid gelling agent is a temperature-resistant, acid-resistant and salt-resistant acid gelling agent synthesized from anionic monomers, cationic monomers, salt-resistant monomers, temperature-resistant monomers and hydrophobic monomers under the action of coupling agents and other treatment agents. .
  • This acid gelling agent has the characteristics of strong viscosity-increasing ability, little influence on shear, stable acid resistance, good temperature resistance, and little secondary damage to the formation. However, the reaction steps are complicated and not conducive to large-scale production.
  • CN113321764A discloses an acid gelling agent and its preparation method and application.
  • the acid gelling agent is synthesized by acrylamide, functional monomers, methacryloyloxyethyltrimethylammonium chloride, and under the action of a chain control agent and an initiator.
  • the acid gelling agent has high thickening performance, good temperature resistance and shear resistance, and can better adapt to the high temperature acidification requirements in deep formations.
  • the reaction steps are complicated and not conducive to large-scale production.
  • CN110982507A discloses an acid gelling agent for acid fracturing and its preparation method and application.
  • the acid gelling agent is synthesized from acrylamide, bio-based cationic monomers, temperature-resistant and salt-resistant monomers and temperature-sensitive monomers.
  • the acid gelling agent has good solubility and thickening properties in acid liquid. However, its temperature resistance is poor and cannot be used in high-temperature wells above 150°C.
  • CN108913119A discloses a gelling agent for fracturing and a preparation method thereof.
  • the gelling agent is synthesized from modified hydroxypropyl guar gum, acid liquid resistance reducing agent, acid liquid corrosion inhibitor and other monomers.
  • the gelling agent has the advantages of high viscosity, low water-insoluble matter, instant dissolution, good fluidity, and fast liquid dispensing during use. However, its temperature resistance is poor and cannot be used in high-temperature wells above 150°C.
  • CN106047333A discloses a high-temperature resistant acid gelling agent and a preparation method thereof.
  • the acid gelling agent is polymerized from three monomers: acrylamide monomer, acryloyloxyethyltrimethylammonium chloride monomer, and a third monomer.
  • the high-temperature-resistant acid gelling agent is simple to synthesize, has high-temperature resistance, salt-resistance, and slow-speed effects, and can be effectively used in high-temperature carbonate rock acidification transformation construction. However, this gelling agent only increases the molecular weight of the molecular chain, but does not improve the rigidity and temperature resistance of the molecular chain structure.
  • CN104388075A discloses an acid gelling agent suitable for high-temperature carbonate rock acidification and a preparation method thereof.
  • the acid gelling agent is a cationic acid gelling agent formed by the copolymerization of two monomers, methacryloyloxyethyltrimethylammonium chloride and acrylamide, initiated by an initiator.
  • the acid gelling agent uses less dosage, is simple to prepare, has low cost and stable performance, and meets the construction requirements for high-temperature carbonate rock acidification.
  • this gelling agent only increases the molecular weight of the molecular chain, but does not improve the rigidity and temperature resistance of the molecular chain structure.
  • CN103923633A discloses a gelled acid acid solution suitable for high-temperature carbonate rock acidification, which contains the following components: acid solution gelling agent 0.6-0.8%, corrosion inhibitor 2-4%, drainage aid 1-2 %, iron ion stabilizer 1-2%, hydrochloric acid 15-22%.
  • This gelled acid acid solution can be used in high-temperature carbonate rock acidification construction and has the effects of high temperature resistance, salt resistance and speed retardation.
  • this invention application only carried out a simple compounding of each treatment agent and did not conduct research and development at the molecular structure level.
  • US20100028434A1 discloses a biopolymer liquid aqueous composition for producing self-gel systems and gels, which contains: acidic water-based medium, 0.1 to 10% by weight of pH gel acid-soluble biopolymer; 0.1 to 10 % by weight of water-soluble molecules having basic characteristics and a pKa between 6.0 and 8.4, or water-soluble residues or sequences of molecules having basic characteristics and a pKa between 6.0 and 8.4.
  • the liquid composition has an adjustable pH value in the range of 5.8-7.4 and forms a stable solid and uniform gel at 10-70°C.
  • the water-soluble molecules are monophosphate binary salts, monosulfonates, monosulfates and monocarboxylates of polyols.
  • the composite gelling agent provided by this invention has not been explored in terms of temperature resistance, and its application range is limited.
  • the purpose of the present invention is to provide a micro-nano-scale spherical modified silicic acid liquid gelling agent and its preparation method and application.
  • the micro-nano spherical modified SiO 2 acid gelling agent provided by the present invention can overcome the problem of degradation of acid gelling agents in the prior art at high temperatures, and has excellent acid resistance and temperature resistance.
  • the present invention first provides a preparation method of micro-nano-scale spherical modified silicic acid liquid gelling agent, which includes the following steps:
  • the macroinitiator is subjected to a third contact reaction with vinyl sulfonate, vinyl quaternary ammonium salt, and N-vinyl pyrrolidone in a third solvent to obtain the Micro-nano spherical modified silica acid liquid gelling agent.
  • the average particle size of the nano-SiO 2 is 10-20 nm.
  • the silane coupling agent includes ⁇ -aminopropyltriethoxysilane (KH550), N-( ⁇ -aminoethyl)- ⁇ -amino One or a combination of propyltrimethoxysilane (KH792) and N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane (KH602).
  • the added amount of the silane coupling agent is 8-12g (that is, the added amount of the silane coupling agent is 80 -120g/L).
  • the amount of nano-SiO 2 added is 1-5g relative to 100 mL of the first solvent (that is, the amount of nano-SiO 2 added is 10-50 g /L), more preferably 1.5-3.5g.
  • the first solvent may include water, such as deionized water or distilled water.
  • the conditions of the first contact reaction are: reaction temperature 25-40°C, reaction time 5-8 h. More preferably, the first contact reaction can be carried out under stirring, and the stirring speed is 200-1200 r/min. After the first contact reaction is completed, the reaction product can be subjected to conventional separation (such as filtration and/or centrifugal separation), washing and other steps. After drying, the surface-modified nano-SiO 2 is obtained.
  • step (1) the drying is freeze-drying, and the freeze-drying conditions are: freezing in liquid nitrogen for 8-12 minutes, freeze-drying under the conditions of -50°C and 9Pa ( Vacuum drying) 24-48h.
  • the silane coupling agent used in the present invention can be on the surface of nano-SiO 2 reaction to prepare modified nano-SiO 2 microspheres with contact sites on the surface.
  • the amount of acrylic acid added is 0.05-0.5 mol relative to 100 mL of the second solvent (that is, the amount of acrylic acid added is 0.5-5 mol/L) , more preferably 0.1-0.3mol.
  • the added amount of the surface-modified nano-SiO 2 is 5-30 g, more preferably 10-20 g.
  • the second solvent may include water, such as deionized water or distilled water.
  • the conditions of the second contact reaction are: reaction temperature 25-40°C, reaction time 5-8 h. More preferably, the second contact reaction can be carried out under stirring at a stirring speed of 600-1000 r/min. After the second contact reaction is completed, the reaction product can be subjected to conventional separation (such as filtration and/or centrifugal separation), washing and other steps. After drying, the macroinitiator is obtained.
  • step (2) the drying is freeze-drying, and the freeze-drying conditions are: freezing in liquid nitrogen for 8-12 minutes, freeze-drying under the conditions of -50°C and 9Pa ( Vacuum drying) 24-48h.
  • the surface-modified nano-SiO 2 can be used as a skeleton, and there are highly active reaction sites on its surface, which can react with acrylic acid on the surface, thereby increasing the number of reaction sites.
  • the activity of the modified nano-SiO 2 is further improved so that after the subsequent addition reaction, a polymer film can be formed on the surface of the modified nano-SiO 2 sphere, thereby improving the resistance of the prepared acid liquid gelling agent. Warm and acid-resistant properties.
  • the vinyl sulfonate (ie, vinyl-containing sulfonate) includes sodium 2-acrylamide-2-methylpropanesulfonate, One or a combination of sodium propyl sulfonate, sodium styrene sulfonate, sodium vinyl sulfonate, etc.
  • the vinyl quaternary ammonium salt includes dimethyldiallylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, trimethylammonium chloride, One or a combination of methyl vinyl ammonium bromide and 4-vinyl benzyl trimethyl ammonium chloride.
  • the added amount of the macroinitiator is 10-20g (that is, the added amount of the macroinitiator is 100 -200g/L).
  • the amount of the vinyl sulfonate added is 0.05-0.5 mol (that is, the amount of the vinyl sulfonate added
  • the amount is 0.5-5.0mol/L), more preferably 0.1-0.3mol.
  • the molar ratio of the vinyl sulfonate, the vinyl quaternary ammonium salt and the N-vinyl pyrrolidone is 1: (1-3) (0.5-1.5), more preferably 1: (1.2-2.3): (0.7-1.3).
  • the oxidizing agent includes ammonium persulfate and/or potassium persulfate, etc.
  • the reducing agent includes sodium bisulfite.
  • the amount of the oxidizing agent is 0.001-0.005 mol relative to 100 mL of the third solvent (that is, the amount of the oxidizing agent is 0.01-0.05 mol/L ).
  • the molar ratio of the oxidant and the reducing agent is 1: (0.5-1.5), more preferably 1: (0.8-1.3).
  • the third solvent may include water, such as deionized water or distilled water.
  • the conditions of the third contact reaction are: reaction temperature 65-80°C, reaction time 3-6h, and the third contact reaction is in a nitrogen atmosphere carried out below. More preferably, the third contact reaction can be carried out under stirring at a stirring speed of 600-800 r/min. After the third contact reaction is completed, the reaction product can be subjected to conventional separation (such as filtration and/or centrifugal separation), washing and other steps. After drying, a micro-nano-sized spherical modified silicic acid liquid gelling agent is obtained.
  • the drying is vacuum drying
  • the drying temperature is 60°C
  • the drying time is 24h
  • the vacuum degree is 9Pa.
  • the vinyl sulfonate monomer, vinyl quaternary ammonium salt monomer, and N-vinyl pyrrolidone monomer can all undergo polymerization reactions through atom transfer radicals in the presence of oxidants and reducing agents; the resulting polymer It will react with the highly active reaction sites on the surface of the modified nano-SiO 2 of the present invention.
  • the steric hindrance effect provided by the macromolecular functional groups on the surface can effectively prevent the polymers from intertwining and adsorbing each other, thereby improving the Temperature resistance of the prepared acid gelling agent.
  • Figure 1 is a preparation process and molecular structure design diagram of the micro-nano-scale spherical modified SiO 2 acid gelling agent of the present invention.
  • the preparation method of the micro-nano-scale spherical modified silicic acid liquid gelling agent provided by the present invention first involves adding active reaction sites on the surface of nano- SiO2 through a silane coupling agent, and then reacts with acrylic acid reaction, thereby increasing the activity of the reaction site, further improving the reactivity of the modified nano-SiO 2 , and then through the amine groups in the vinyl quaternary ammonium salt monomer, vinyl sulfonate monomer and N-vinyl pyrrolidone monomer
  • the vinyl quaternary ammonium salt monomer and vinyl sulfonate monomer used in the present invention can, on the one hand, provide macromolecular side chains and improve the steric hindrance of the prepared polymer.
  • the anti-polyelectrolyte effect of the presence of anions and cations can also better maintain the stability of the polymer molecular chain.
  • the N-vinylpyridine used in the present invention The rrolidone monomer further improves the branched rigidity of the prepared polymer molecular chain.
  • the second aspect of the present invention provides a micro-nano-sized spherical modified silicic acid liquid gelling agent, which is prepared by the above preparation method.
  • the average particle size of the micro-nano-sized spherical modified silicic acid liquid gelling agent is 500-2000 nm, more preferably 500-900 nm.
  • the micro-nano-sized spherical modified silicic acid liquid gelling agent is sheared in a 20% HCl aqueous solution with a mass fraction of 180°C and 170 s -1 for 1 hour. Its apparent viscosity is greater than 45mPa ⁇ s.
  • the third aspect of the present invention provides an application of the above-mentioned micro-nano-scale spherical modified silica acid liquid gelling agent in acid fracturing.
  • the target reservoir temperature of the acid fracturing is 150°C or above, and more preferably 180°C or above.
  • the micro-nano-scale spherical modified silicic acid liquid gelling agent of the present invention is composed of micro-nano-scale spherical SiO 2 and an organic polymer supported on the micro-nano-scale spherical SiO 2 .
  • the present invention uses micro-nano-scale spherical modified SiO2 as an excellent template, wraps a layer of polymer on the surface, introduces macromolecular side chains and rigid main chains, and improves the temperature resistance and acid resistance of the acid liquid gelling agent.
  • the gelled acid system formed by the acid gel of the present invention can be used in high-temperature reservoirs (180°C or even above).
  • the micro-nano-scale spherical modified silica acid liquid gelling agent of the present invention has excellent temperature resistance and acid resistance, and overcomes the problem of degradation of the acid liquid gelling agent of the prior art at high temperatures. Liquid gelling agents can support oil and gas pathways in specific formations, thereby improving oil recovery.
  • micro-nano-scale spherical modified SiO 2 acid gelling agent provided by the present invention includes the following beneficial effects:
  • the micro-nano spherical modified SiO 2 acid gelling agent of the present invention has rigid skeleton particles, which can enter the target formation pores and support oil and gas channels;
  • the polymer molecular chain of the micro-nano-sized spherical modified SiO 2 acid gelling agent of the present invention has macromolecular side chains and functional groups, which can improve its temperature resistance;
  • the reaction conditions of the micro-nano-sized spherical modified SiO 2 acid gelling agent of the present invention are easy to control, the reaction process is relatively stable, and industrialization is easy to achieve.
  • Figure 1 is a preparation process and molecular structure design diagram of the micro-nano-scale spherical modified SiO 2 acid gelling agent of the present invention.
  • the nanosilica used is provided by Beijing Dekedao Gold Technology Co., Ltd.
  • silane coupling agent N-vinylpyrrolidone, vinyl sulfonate, and vinyl quaternary ammonium salt used were all provided by Sinopharm Shanghai Test Group.
  • the potassium persulfate, ammonium persulfate, and sodium bisulfite used were all provided by Aladdin Reagent Co., Ltd.
  • the average particle size of the acid gelling agent was measured by a Malvern Zetasizer 3000 potential-particle size tester.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • the average particle size of NSGA-1 was measured to be 532.95nm.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • step (3) In a 500mL three-necked round-bottomed flask equipped with a thermometer, stirring rod and nitrogen guide tube, add 29.48g of the macroinitiator obtained in step (2), 57.64g (0.4mol) sodium allyl sulfonate, 191.08 g (0.92mol) methacryloyloxyethyltrimethylammonium chloride and 44.4g (0.4mol) N-vinylpyrrolidone were dispersed in 200mL deionized water, heated to 80°C, and 2.7g (0.01mol) were added in sequence Potassium persulfate and 1.35g (0.013mol) sodium bisulfite were reacted for 6 hours at a stirring speed of 800r/min; after the reaction was completed, filtered, washed, and dried to obtain the micro-nano-scale spherical modified silica liquid gel.
  • the coagulant is named NSGA-2 (Nano Spheres of Gelling Agent-2).
  • the average particle size of NSGA-2 was measured to be 732.95nm.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • step (3) In a 500mL three-necked round-bottomed flask equipped with a thermometer, stirring rod and nitrogen guide tube, add 22.4g of the macroinitiator obtained in step (2), 41.23g (0.2mol) sodium styrene sulfonate, 41.52g (0.25mol) trimethylvinyl ammonium bromide and 15.54g (0.14mol) N-vinylpyrrolidone were dispersed in 200mL deionized water, heated to 80°C, and 2.7g (0.01mol) potassium persulfate and 1.35g were added in sequence.
  • the macroinitiator obtained in step (2) 41.23g (0.2mol) sodium styrene sulfonate, 41.52g (0.25mol) trimethylvinyl ammonium bromide and 15.54g (0.14mol) N-vinylpyrrolidone were dispersed in 200mL deionized water, heated to 80°C, and 2.7g (0
  • the average particle size of NSGA-3 was measured to be 892.43nm.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • step (3) In a 500mL three-necked round-bottomed flask equipped with a thermometer, stirring rod and nitrogen guide tube, add 37.2g of the macroinitiator obtained in step (2), 110.58g (0.85mol) sodium vinyl sulfonate, 451.98g (2.13mol) 4-vinylbenzyltrimethylammonium chloride and 133.2g (1.2mol) N-vinylpyrrolidone were dispersed in 200mL deionized water, heated to 80°C, and 2.7g (0.01mol) persulfuric acid was added in sequence.
  • NSGA-4 Nano Spheres of Gelling Agent-4
  • the average particle size of NSGA-4 was measured to be 1035.28nm.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • step (3) In a 500mL three-necked round-bottomed flask equipped with a thermometer, stirring rod and nitrogen guide tube, add 31.64g of the macroinitiator obtained in step (2), 160.46g (0.7mol) 2-acrylamide-2-methyl Disperse sodium propanesulfonate, 124.49g (0.77mol) dimethyldiallylammonium chloride, and 38.85g (0.35mol) N-vinylpyrrolidone into 200mL deionized water, heat it to 80°C, and add 2.7g in sequence (0.01mol) potassium persulfate and 1.35g (0.013mol) sodium bisulfite, react for 6 hours at a stirring speed of 800r/min; after the reaction is completed, filter, wash and dry to obtain the micro-nano-scale spherical modified dioxide Silicic acid liquid gelling agent, named NSGA-5 (Nano Spheres of Gelling Agent-5).
  • NSGA-5 Nano Spheres of Gelling Agent-5
  • the average particle size of NSGA-5 was measured to be 1486.38nm.
  • This embodiment provides a micro-nano-scale spherical modified silicic acid liquid gelling agent, which is prepared by the following method:
  • step (3) In a 500mL three-necked round-bottomed flask equipped with a thermometer, stirring rod and nitrogen guide tube, add 20.5g of the macroinitiator obtained in step (2), 20.17g (0.14mol) sodium allyl sulfonate, 78.93 g (0.38mol) methacryloyloxyethyltrimethylammonium chloride, 9.32g (0.084mol) N-vinylpyrrolidone were dispersed into 200mL deionized In water, raise the temperature to 80°C, add 2.7g (0.01mol) potassium persulfate and 1.35g (0.013mol) sodium bisulfite in sequence, and react for 6 hours at a stirring speed of 800r/min; after the reaction is completed, filter, wash, and dry to obtain
  • the micro-nano spherical modified silicic acid liquid gelling agent is named NSGA-6 (Nano Spheres of Gelling Agent-6).
  • the average particle size of NSGA-6 was measured to be 1967.47nm.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (1), the silane coupling agent KH550 is not added, and other raw materials and dosage and preparation The process was the same as in Example 1, and the acid gelling agent D1 was obtained, and its average particle size was measured to be 3.28 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (2), acrylic acid (AA) is not added, and other raw materials and dosages as well as the preparation process are not added.
  • the acid liquid gelling agent D2 was obtained in the same manner as in Example 1, and its average particle size was measured to be 15.28 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (3), the sodium 2-acrylamide-2-methylpropanesulfonate is The addition amount was changed to 0.48g, and other raw materials, dosages, and preparation processes were the same as in Example 1.
  • the acid gelling agent D3 was obtained, and its average particle size was measured to be 1.52 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (3), the amount of N-vinylpyrrolidone is changed to 1.16g, and the other The raw materials, dosage and preparation process were the same as those in Example 1, and the acid gelling agent D4 was obtained, and its average particle size was measured to be 1.24 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (3), dimethyl diallylammonium chloride is not added.
  • the raw materials, dosage and preparation process were the same as those in Example 1, and the acid gelling agent D5 was obtained, and its average particle size was measured to be 1.12 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1, except that in step (3), dimethyldiallylammonium chloride is replaced by propylene 1.32 mol of amide, other raw materials, dosage and preparation process were the same as in Example 1, and the acid gelling agent D6 was obtained, and its average particle size was measured to be 0.98 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1. The difference is that in step (3), N-vinylpyrrolidone is replaced by 0.78 mol of styrene, and the other The raw materials, dosage and preparation process were the same as those in Example 1, and the acid gelling agent D7 was obtained, and its average particle size was measured to be 2.26 ⁇ m.
  • This comparative example provides an acid gelling agent, which is basically prepared according to the method of Example 1, except that in step (3), sodium 2-acrylamide-2-methylpropanesulfonate is Replaced with 0.6 mol of styrene, and other raw materials, dosages, and preparation processes were the same as in Example 1 to obtain acid gelling agent D8, whose average particle size was measured to be 2.46 ⁇ m.
  • This test example conducts experiments on the acid gelling agents provided in Examples 1-6 and Comparative Examples 1-8, and tests their apparent viscosity in a 20% HCl aqueous solution with a mass fraction of 20% at room temperature and 180°C. The results are as shown in the table 1 shown.
  • normal temperature is 25°C.
  • the micro-nano-scale spherical modified silicic acid liquid gelling agent prepared in the embodiment of the present invention is sheared in a 20% HCl aqueous solution with a mass fraction of 180° C. and 170 s -1 1h, the apparent viscosity is greater than 45mPa ⁇ s, therefore, it has excellent temperature resistance and acid resistance.

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Abstract

本发明提供了一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用。该微纳米级球形改性二氧化硅酸液胶凝剂的制备方法为：使纳米SiO2和硅烷偶联剂接触反应得到表面改性的纳米SiO2；使表面改性的纳米SiO2和丙烯酸接触反应得到大分子引发剂；在氧化剂和还原剂存在下，将大分子引发剂与乙烯基磺酸盐、乙烯基季铵盐、N-乙烯基吡咯烷酮接触反应，得到微纳米级球形改性二氧化硅酸液胶凝剂。本发明的微纳米级球形改性二氧化硅酸液胶凝剂是通过上述方法制备得到的。本发明还提供了该酸液胶凝剂在酸化压裂中的应用。本发明的酸液胶凝剂可达到180℃以上的抗温性能，可在特定地层支撑油气通道，进而提高采收率。

Description

一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用 技术领域
本发明涉及油气田开发技术领域，具体涉及一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用。
背景技术
酸化压裂是油气田增产技术中最为主要的增产措施。其通常使用酸液对目标地层进行溶蚀或刻蚀处理，以形成油气流通通道，进而实现提高增产的目的。研究表明，酸化压裂作业的主要影响因素是缝的导流能力和溶蚀裂缝长度。降低酸液的溶蚀速率是保证酸化作业质量的重要因素之一。在现场作业中，一般采用提高酸液粘度来降低酸液的溶蚀速率，这是由于分子链网架结构可以降低氢离子的扩散速率，从而降低酸液对岩石表面的腐蚀效率。因此，酸液胶凝剂的研究成为了油气田开发领域的重要课题之一。
近年来，随着油气井开发难度逐渐增加，深井、超深井数量逐渐增多，井底温度也随之增加。在高温下，聚合物分子容易受到热降解、热氧降解等因素的影响而导致聚合物分子链断裂。同时，氢离子在高温下的分子热运动会加剧，促进分子链的降解，破坏钻井液的增粘性能。根据产品调研，有些公司研发的大部分胶凝酸面临着耐酸性能较差、抗温性能较弱的问题；有些公司研发的抗高温酸液用缓凝酸具有较为优异的抗温、耐酸性能，但其产品价格较高，影响了油田企业的生产效益。
目前，提高聚合物分子的抗温性能主要有以下几种方式：1、引入大分子刚性侧链；2、提高主链的刚性；3、引入具有耐水解官能团的单体；4、引入疏水缔合单体；5、引入刚性骨架结构。大多数研究人员一般通过引入大分子侧链或引入耐水解官能团来提高酸液胶凝剂的抗温性能，这主要是由于聚合机理明确，易于合成。
CN113563505A公开了一种耐温耐酸抗盐型酸液胶凝剂及其制备方法。该酸液胶凝剂为阴离子单体、阳离子单体、抗盐单体、耐温单体及疏水单体在偶联剂等处理剂作用下合成的耐温耐酸抗盐型酸液胶凝剂。该酸液胶凝剂具有增黏能力强、受剪切影响小、耐酸稳定，耐温性良好，对地层二次伤害小等特点。但其反应步骤较为繁琐，不利于大规模生产。
CN113321764A公开了一种酸液胶凝剂及其制备方法和应用。该酸液胶凝剂通过丙烯酰胺、功能性单体、甲基丙烯酰氧乙基三甲基氯化铵在链控制剂、引发剂的作用下合成。该酸液胶凝剂的稠化性能高、耐温抗剪切性能好、能较好地适应地层深部的高温酸化要求。但其反应步骤较为繁琐，不利于大规模生产。
CN110982507A公开了一种用于酸化压裂的酸液胶凝剂及其制备方法和应用。该酸液胶凝剂是由丙烯酰胺、生物基阳离子单体、耐温抗盐单体和温敏单体合成得到的。该酸液胶凝剂在酸液中具有良好的溶解性和增粘性能。但其抗温性能较差，不能用于150℃以上的高温井中。
CN108913119A公开了一种压裂用胶凝剂及其制备方法。该胶凝剂由改性羟丙基瓜胶、酸液降阻剂、酸液缓蚀剂等单体合成。该胶凝剂具有高粘、低水不溶物、速溶、流动性好的优点，使用过程中配液速度快。但其抗温性能较差，不能用于150℃以上的高温井中。
CN106047333A公开了一种耐高温酸液胶凝剂及其制备方法。该酸液胶凝剂由丙烯酰胺单体、丙烯酰氧乙基三甲基氯化铵单体、第三单体三种单体聚合而成。该耐高温酸液胶凝剂的合成简易，具有抗高温、抗盐、缓速的作用，可有效应用于高温碳酸盐岩酸化改造施工。但该胶凝剂只是提高分子链的分子量，并未提高分子链结构的刚性和抗温性能。
CN104388075A公开了一种适用于高温碳酸盐岩酸化用的酸液胶凝剂及其制备方法。该酸液胶凝剂为甲基丙烯酰氧乙基三甲基氯化铵与丙烯酰胺两种单体经引发剂引发共聚合成的阳离子酸液胶凝剂。该酸液胶凝剂用量少配制简单，成本低，性能稳定，满足高温碳酸盐岩酸化的施工要求。但该胶凝剂只是提高分子链的分子量，并未提高分子链结构的刚性和抗温性能。
CN103923633A公开了一种适用于高温碳酸盐岩酸化用的胶凝酸酸液，其含有以下成分：酸液胶凝剂0.6-0.8％、缓蚀剂2-4％、助排剂1-2％、铁离子稳定剂1-2％、盐酸15-22％。该胶凝酸酸液可以应用于高温碳酸盐岩酸化施工中，具有抗高温、抗盐、缓速的作用。但该发明申请只对各处理剂进行了简单的复配，没有进行分子结构层面的研发。
US20100028434A1公开了一种用于生产自凝胶系统和凝胶的生物聚合物液体水性组合物，其包含：酸性水基介质、0.1至10重量％的pH凝胶酸可溶性生物聚合物；0.1至10重量％的具有碱性特征且pKa介于6.0至8.4之间的水溶性分子，或具有碱性特征且pKa介于6.0至8.4之间的分子的水溶性残基或序列。该液体组合物的pH值可调节范围为5.8-7.4，并在10-70℃形成稳定的固体和均匀凝胶。其中，水溶性分子为多元醇的单磷酸盐二元盐、单磺酸盐、单硫酸盐及单羧酸盐等。该发明提供的复合胶凝剂在耐温方面未作探索，且适用范围有限。
因此，如何制备出抗高温酸液用酸液胶凝剂是当前的研究重点及难点。
发明内容
为解决上述技术问题，本发明的目的在于提供一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用。本发明提供的微纳米级球形改性SiO2酸液胶凝剂能够克服现有技术的酸液胶凝剂高温下降解的问题，其具有优异的抗酸、抗温性能。
为了实现上述目的，本发明首先提供了一种微纳米级球形改性二氧化硅酸液胶凝剂的制备方法，其包括以下步骤：
(1)使纳米SiO2和硅烷偶联剂在第一溶剂中进行第一接触反应，至少经干燥后，得到表面改性的纳米SiO2；
(2)使所述表面改性的纳米SiO2和丙烯酸在第二溶剂中进行第二接触反应，至少经干燥后，得到大分子引发剂；
(3)在氧化剂和还原剂存在下，将所述大分子引发剂与乙烯基磺酸盐、乙烯基季铵盐、N-乙烯基吡咯烷酮在第三溶剂中进行第三接触反应，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂。
在上述制备方法中，优选地，在步骤(1)中，所述纳米SiO2的平均粒径为10-20nm。
在上述制备方法中，优选地，在步骤(1)中，所述硅烷偶联剂包括γ-氨丙基三乙氧基硅烷(KH550)、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(KH792)以及N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷(KH602)等中的一种或几种的组合。
在上述制备方法中，优选地，在步骤(1)中，相对于100mL第一溶剂，所述硅烷偶联剂的加量为8-12g(即，所述硅烷偶联剂的加量为80-120g/L)。
在上述制备方法中，优选地，在步骤(1)中，相对于100mL第一溶剂，所述纳米SiO2的加量为1-5g(即，所述纳米SiO2的加量为10-50g/L)，更优选为1.5-3.5g。
在上述制备方法中，优选地，在步骤(1)中，所述第一溶剂可以包括水，例如去离子水或蒸馏水等。
在上述制备方法中，优选地，在步骤(1)中，所述第一接触反应的条件为：反应温度25-40℃，反应时间5-8h。更优选地，所述第一接触反应可以在搅拌下进行，搅拌速度为200-1200r/min。在所述第一接触反应结束后，可以对反应产物进行常规的分离(例如过滤和/或离心分离)、洗涤等步骤。之后经过干燥后，得到所述表面改性的纳米SiO2。
在上述制备方法中，优选地，在步骤(1)中，所述干燥为冷冻干燥，所述冷冻干燥的条件为：液氮冷冻8-12min，在-50℃、9Pa的条件下冷冻干燥(真空干燥)24-48h。
在本发明的制备方法的步骤(1)中，本发明采用的硅烷偶联剂可在纳米SiO2表面 反应，制备得到表面具有接触位点的改性纳米SiO2微球。
在上述制备方法中，优选地，在步骤(2)中，相对于100mL第二溶剂，所述丙烯酸的加量为0.05-0.5mol(即，所述丙烯酸的加量为0.5-5mol/L)，更优选为0.1-0.3mol。
在上述制备方法中，优选地，在步骤(2)中，相对于100mL第二溶剂，所述表面改性的纳米SiO2的加量为5-30g，更优选为10-20g。
在上述制备方法中，优选地，在步骤(2)中，所述第二溶剂可以包括水，例如去离子水或蒸馏水等。
在上述制备方法中，优选地，在步骤(2)中，所述第二接触反应的条件为：反应温度25-40℃，反应时间5-8h。更优选地，所述第二接触反应可以在搅拌下进行，搅拌速度为600-1000r/min。在所述第二接触反应结束后，可以对反应产物进行常规的分离(例如过滤和/或离心分离)、洗涤等步骤。之后经过干燥后，得到所述大分子引发剂。
在上述制备方法中，优选地，在步骤(2)中，所述干燥为冷冻干燥，所述冷冻干燥的条件为：液氮冷冻8-12min，在-50℃、9Pa的条件下冷冻干燥(真空干燥)24-48h。
在本发明的制备方法的步骤(2)中，所述表面改性的纳米SiO2可作为骨架，其表面存在活性较高的反应位点，可在表面与丙烯酸发生反应，进而增加反应位点的活性，进一步提高改性纳米SiO2的反应活性，以使其经过后续的加成反应后，可在改性纳米SiO2球表面形成聚合物膜，提高制备得到的酸液胶凝剂的抗温、抗酸性能。
在上述制备方法中，优选地，在步骤(3)中，所述乙烯基磺酸盐(即，含有乙烯基的磺酸盐)包括2-丙烯酰胺-2-甲基丙磺酸钠、烯丙基磺酸钠、苯乙烯磺酸钠和乙烯基磺酸钠等中的一种或几种的组合。
在上述制备方法中，优选地，在步骤(3)中，所述乙烯基季铵盐包括二甲基二烯丙基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵、三甲基乙烯基溴化铵和4-乙烯基苄基三甲基氯化铵等中的一种或几种的组合。
在上述制备方法中，优选地，在步骤(3)中，相对于100mL第三溶剂，所述大分子引发剂的加量为10-20g(即，所述大分子引发剂的加量为100-200g/L)。
在上述制备方法中，优选地，在步骤(3)中，相对于100mL第三溶剂，所述乙烯基磺酸盐的加量为0.05-0.5mol(即，所述乙烯基磺酸盐的加量为0.5-5.0mol/L)，更优选为0.1-0.3mol。
在上述制备方法中，优选地，在步骤(3)中，所述乙烯基磺酸盐、所述乙烯基季铵盐与所述N-乙烯基吡咯烷酮的摩尔比为1：(1-3)：(0.5-1.5)，更优选为1：(1.2-2.3)：(0.7-1.3)。
在上述制备方法中，优选地，在步骤(3)中，所述氧化剂包括过硫酸铵和/或过硫酸钾等。
在上述制备方法中，优选地，在步骤(3)中，所述还原剂包括亚硫酸氢钠。
在上述制备方法中，优选地，在步骤(3)中，相对于100mL第三溶剂，所述氧化剂的加量为0.001-0.005mol(即，所述氧化剂的加量为0.01-0.05mol/L)。
在上述制备方法中，优选地，在步骤(3)中，所述氧化剂和所述还原剂的摩尔比为1：(0.5-1.5)，更优选为1：(0.8-1.3)。
在上述制备方法中，优选地，在步骤(3)中，所述第三溶剂可以包括水，例如去离子水或蒸馏水等。
在上述制备方法中，优选地，在步骤(3)中，所述第三接触反应的条件为：反应温度65-80℃，反应时间3-6h，且所述第三接触反应是在氮气气氛下进行的。更优选地，所述第三接触反应可以在搅拌下进行，搅拌速度为600-800r/min。在所述第三接触反应结束后，可以对反应产物进行常规的分离(例如过滤和/或离心分离)、洗涤等步骤。之后经过干燥后，得到微纳米级球形改性二氧化硅酸液胶凝剂。
在上述制备方法中，优选地，在步骤(3)中，所述干燥为真空干燥，干燥温度为60℃，干燥时间为24h，真空度为9Pa。
在本发明中，乙烯基季铵盐单体、乙烯基磺酸盐单体及N-乙烯基吡咯烷酮单体均是利用C＝C双键打开后进行反应。所述乙烯基磺酸盐单体、乙烯基季铵盐单体、N-乙烯基吡咯烷酮单体均可在氧化剂和还原剂存在的条件下通过原子转移自由基发生聚合反应；所生成的聚合物会与本发明改性后的纳米SiO2表面的高活性反应位点进行反应，其表面所具有的大分子官能团所提供的空间位阻效应可有效防止聚合物之间相互缠绕、吸附，进而提高制备得到的酸液胶凝剂的抗温性。
图1为本发明的微纳米级球形改性SiO2酸液胶凝剂的制备流程及分子结构设计图。如图1所示，本发明提供的微纳米级球形改性二氧化硅酸液胶凝剂的制备方法，首先是通过硅烷偶联剂在纳米SiO2表面增加活性反应位点，然后与丙烯酸发生反应，进而增加反应位点的活性，进一步提高改性纳米SiO2的反应活性，再通过乙烯基季铵盐单体、乙烯基磺酸盐单体及N-乙烯基吡咯烷酮单体中的胺基与羧基之间的反应引入C＝C，可以有效降低由于固体颗粒存在所带来的空间位阻效应，从而导致单体在固体颗粒表面接枝率低的问题。同时，本发明采用的乙烯基季铵盐单体、乙烯基磺酸盐单体一方面可以提供大分子侧链，提高制备得到的聚合物的空间位阻。另一方面，阴阳离子存在的反聚电解质效应，也能够较好地保持聚合物分子链的稳定。并且本发明采用的N-乙烯基吡 咯烷酮单体更进一步提高了制备得到的聚合物分子链的支链刚性。
本发明第二方面提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过上述的制备方法制备得到的。
根据本发明的具体实施方式，优选地，所述微纳米级球形改性二氧化硅酸液胶凝剂的平均粒径为500-2000nm，更优选为500-900nm。
根据本发明的具体实施方式，优选地，所述微纳米级球形改性二氧化硅酸液胶凝剂在质量分数为20％HCl水溶液中，在180℃、170s-1条件下剪切1h，其表观粘度大于45mPa·s。
本发明第三方面提供了一种上述的微纳米级球形改性二氧化硅酸液胶凝剂在酸化压裂中的应用。
在上述应用中，优选地，所述酸化压裂的目标储层温度为150℃以上，更优选为180℃以上。
本发明的微纳米级球形改性二氧化硅酸液胶凝剂由微纳米级球形SiO2以及负载在所述微纳米级球形SiO2上的有机高分子聚合物构成。本发明采用微纳米级球形改性SiO2作为优良的模板，在表面包裹一层聚合物，引入了大分子侧链和刚性主链，提高了酸液胶凝剂的抗温、抗酸性能。本发明的酸液凝胶剂形成的胶凝酸体系可应用于高温储层(180℃甚至以上)中，其表观粘度受高温作用影响较小，且在高剪切速率条件下仍然维持较高表观粘度，进而达到延缓H+释放速度，降低酸岩反应速率，增加酸液有效作用距离，提高高温碳酸盐岩储层酸化改造效果的目的。因此，本发明的微纳米级球形改性二氧化硅酸液胶凝剂具有优异的抗温、抗酸性能，克服了现有技术的酸液胶凝剂高温下降解的问题，本发明的酸液胶凝剂可在特定地层支撑油气通道，进而提高采收率。
综上所述，本发明提供的微纳米级球形改性SiO2酸液胶凝剂包括如下有益效果：
(1)与传统的酸液胶凝剂相比，本发明的微纳米级球形改性SiO2酸液胶凝剂具有刚性骨架颗粒，可进入目标地层孔隙，支撑油气通道；
(2)与传统的酸液胶凝剂相比，本发明的微纳米级球形改性SiO2酸液胶凝剂的聚合物分子链具有大分子侧链及官能团，可提高其抗温性能；
(3)与传统的酸液胶凝剂相比，本发明的微纳米级球形改性SiO2酸液胶凝剂反应条件容易控制，反应过程相对稳定，易实现工业化。
附图说明
图1为本发明的微纳米级球形改性SiO2酸液胶凝剂的制备流程及分子结构设计图。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中：
所采用的纳米二氧化硅由北京德科岛金科技有限公司提供。
所采用的硅烷偶联剂、N-乙烯基吡咯烷酮、乙烯基磺酸盐、乙烯基季铵盐均由国药沪试集团提供。
所采用的过硫酸钾、过硫酸铵、亚硫酸氢钠均由阿拉丁试剂有限公司提供。
酸液胶凝剂的平均粒径由马尔文Zetasizer 3000电位-粒度测试仪进行测试。
实施例1
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入68g纳米SiO2(20nm)，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加200g硅烷偶联剂KH550并在1200r/min条件下搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻10min，在-50℃、9Pa条件下真空干燥24h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入0.6mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻10min，在-50℃、9Pa条件下真空干燥24h，得到大分子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将38.6g步骤(2)得到的大分子引发剂、137.54g(0.6mol)2-丙烯酰胺-2-甲基丙磺酸钠、213.41g(1.32mol)二甲基二烯丙基氯化铵、86.58g(0.78mol)N-乙烯基吡咯烷酮分散至200mL去离子水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥(干燥为真空干燥，干燥温度为60℃，干燥时间为24h，真空度为9Pa)，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-1(Nano Spheres of Gelling Agent-1)。
测得NSGA-1的平均粒径为532.95nm。
实施例2
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入32g纳米SiO2，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加160g硅烷偶联剂KH792并200r/min搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻8min，在-50℃、9Pa条件下真空干燥48h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入0.2mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻10min，在-50℃、9Pa条件下真空干燥24h，得到大分子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将29.48g步骤(2)得到的大分子引发剂、57.64g(0.4mol)烯丙基磺酸钠、191.08g(0.92mol)甲基丙烯酰氧乙基三甲基氯化铵、44.4g(0.4mol)N-乙烯基吡咯烷酮分散至200mL去离子水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-2(Nano Spheres of Gelling Agent-2)。
测得NSGA-2的平均粒径为732.95nm。
实施例3
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入50g纳米SiO2，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加240g硅烷偶联剂KH602并1000r/min搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻12min，在-50℃、9Pa条件下真空干燥24h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入0.4mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻12min，在-50℃、9Pa条件下真空干燥36h，得到大分 子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将22.4g步骤(2)得到的大分子引发剂、41.23g(0.2mol)苯乙烯磺酸钠、41.52g(0.25mol)三甲基乙烯基溴化铵、15.54g(0.14mol)N-乙烯基吡咯烷酮分散至200mL去离子水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-3(Nano Spheres of Gelling Agent-3)。
测得NSGA-3的平均粒径为892.43nm。
实施例4
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入96g纳米SiO2，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加190g硅烷偶联剂KH550并800r/min搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻12min，在-50℃、9Pa条件下真空干燥30h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入1.0mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻12min，在-50℃、9Pa条件下真空干燥30h，得到大分子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将37.2g步骤(2)得到的大分子引发剂、110.58g(0.85mol)乙烯基磺酸钠、451.98g(2.13mol)4-乙烯基苄基三甲基氯化铵、133.2g(1.2mol)N-乙烯基吡咯烷酮分散至200mL去离子水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-4(Nano Spheres of Gelling Agent-4)。
测得NSGA-4的平均粒径为1035.28nm。
实施例5
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入24g纳米SiO2，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加210g硅烷偶联剂KH792并400r/min搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻11min，在-50℃、9Pa条件下真空干燥33h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入0.12mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻11min，在-50℃、9Pa条件下真空干燥33h，得到大分子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将31.64g步骤(2)得到的大分子引发剂、160.46g(0.7mol)2-丙烯酰胺-2-甲基丙磺酸钠、124.49g(0.77mol)二甲基二烯丙基氯化铵、38.85g(0.35mol)N-乙烯基吡咯烷酮分散至200mL去离子水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-5(Nano Spheres of Gelling Agent-5)。
测得NSGA-5的平均粒径为1486.38nm。
实施例6
本实施例提供了一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过以下方法制备得到的：
(1)在2000mL去离子水中加入60g纳米SiO2，磁力搅拌20min使其均匀分散在去离子水中，得到纳米SiO2悬浮液；在所述纳米SiO2悬浮液中缓慢滴加220g硅烷偶联剂KH602并300r/min搅拌使其溶解；然后继续搅拌在40℃反应8h，过滤，液氮冷冻10min，在-50℃、9Pa条件下真空干燥44h，得到表面改性的纳米SiO2；
(2)在200mL去离子水中加入0.5mol丙烯酸(AA)，得到AA溶液；将39.2g步骤(1)得到的表面改性的纳米SiO2加入所述AA溶液中；在40℃、1000r/min搅拌速度下反应8h，过滤，液氮冷冻10min，在-50℃、9Pa条件下真空干燥44h，得到大分子引发剂；
(3)在装有温度计、搅拌杆和氮气引导管的500mL三口圆底烧瓶中，将20.5g步骤(2)得到的大分子引发剂、20.17g(0.14mol)烯丙基磺酸钠、78.93g(0.38mol)甲基丙烯酰氧乙基三甲基氯化铵、9.32g(0.084mol)N-乙烯基吡咯烷酮分散至200mL去离子 水中，升温至80℃，依次加入2.7g(0.01mol)过硫酸钾和1.35g(0.013mol)亚硫酸氢钠，800r/min搅拌速度下反应6h；反应完毕后，过滤、洗涤、干燥，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂，命名为NSGA-6(Nano Spheres of Gelling Agent-6)。
测得NSGA-6的平均粒径为1967.47nm。
对比例1
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(1)中，不加入硅烷偶联剂KH550，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D1，测得其平均粒径为3.28μm。
对比例2
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(2)中，不加入丙烯酸(AA)，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D2，测得其平均粒径为15.28μm。
对比例3
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，2-丙烯酰胺-2-甲基丙磺酸钠的加量改为0.48g，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D3，测得其平均粒径为1.52μm。
对比例4
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，N-乙烯基吡咯烷酮的加量改为1.16g，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D4，测得其平均粒径为1.24μm。
对比例5
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，不加入二甲基二烯丙基氯化铵，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D5，测得其平均粒径为1.12μm。
对比例6
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，将二甲基二烯丙基氯化铵替换为丙烯酰胺1.32mol，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D6，测得其平均粒径为0.98μm。
对比例7
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，将N-乙烯基吡咯烷酮替换为苯乙烯0.78mol，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D7，测得其平均粒径为2.26μm。
对比例8
本对比例提供了一种酸液胶凝剂，其是基本按照实施例1的方法制备的，不同的是，在步骤(3)中，将2-丙烯酰胺-2-甲基丙磺酸钠替换为苯乙烯0.6mol，其他原料和用量以及制备过程均与实施例1相同，得到酸液胶凝剂D8，测得其平均粒径为2.46μm。
测试例
本测试例对实施例1-6和对比例1-8提供的酸液胶凝剂进行实验，测试其分别在常温、180℃的质量分数为20％HCl水溶液中的表观粘度，结果如表1所示。
表1不同类型酸液胶凝剂的性能参数
其中，常温为25℃。
由表1可以明显看出，本发明实施例制备得到的微纳米级球形改性二氧化硅酸液胶凝剂在质量分数为20％HCl水溶液中，在180℃、170s-1条件下剪切1h，表观粘度大于 45mPa·s，因此，具有优异的抗温、抗酸性能。

Claims (20)

  1. 一种微纳米级球形改性二氧化硅酸液胶凝剂的制备方法，其包括以下步骤：
    (1)使纳米SiO2和硅烷偶联剂在第一溶剂中进行第一接触反应，至少经干燥后，得到表面改性的纳米SiO2；
    (2)使所述表面改性的纳米SiO2和丙烯酸在第二溶剂中进行第二接触反应，至少经干燥后，得到大分子引发剂；
    (3)在氧化剂和还原剂存在下，将所述大分子引发剂与乙烯基磺酸盐、乙烯基季铵盐、N-乙烯基吡咯烷酮在第三溶剂中进行第三接触反应，得到所述的微纳米级球形改性二氧化硅酸液胶凝剂。
  2. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述纳米SiO2的平均粒径为10-20nm。
  3. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述硅烷偶联剂包括γ-氨丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷以及N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷中的一种或几种的组合。
  4. 根据权利要求1所述的制备方法，其中，在步骤(1)中，相对于100mL第一溶剂，所述硅烷偶联剂的加量为8-12g。
  5. 根据权利要求1所述的制备方法，其中，在步骤(1)中，相对于100mL第一溶剂，所述纳米SiO2的加量为1-5g。
  6. 根据权利要求1所述的制备方法，其中，在步骤(1)中，所述第一接触反应的条件为：反应温度25-40℃，反应时间5-8h；优选地，所述第一接触反应在搅拌下进行，搅拌速度为200-1200r/min；
    优选地，在步骤(1)中，所述干燥为冷冻干燥，所述冷冻干燥的条件为：液氮冷冻8-12min，在-50℃、9Pa的条件下冷冻干燥24-48h。
  7. 根据权利要求1所述的制备方法，其中，在步骤(2)中，相对于100mL第二溶剂，所述丙烯酸的加量为0.05-0.5mol。
  8. 根据权利要求1所述的制备方法，其中，在步骤(2)中，相对于100mL第二溶剂，所述表面改性的纳米SiO2的加量为5-30g。
  9. 根据权利要求1所述的制备方法，其中，在步骤(2)中，所述第二接触反应的条件为：反应温度25-40℃，反应时间5-8h；优选地，所述第二接触反应在搅拌下进行，搅拌速度为600-1000r/min；
    优选地，在步骤(2)中，所述干燥为冷冻干燥，所述冷冻干燥的条件为：液氮冷 冻8-12min，在-50℃、9Pa的条件下冷冻干燥24-48h。
  10. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述乙烯基磺酸盐包括2-丙烯酰胺-2-甲基丙磺酸钠、烯丙基磺酸钠、苯乙烯磺酸钠和乙烯基磺酸钠中的一种或几种的组合。
  11. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述乙烯基季铵盐包括二甲基二烯丙基氯化铵、甲基丙烯酰氧乙基三甲基氯化铵、三甲基乙烯基溴化铵和4-乙烯基苄基三甲基氯化铵中的一种或几种的组合。
  12. 根据权利要求1所述的制备方法，其中，在步骤(3)中，相对于100mL第三溶剂，所述大分子引发剂的加量为10-20g。
  13. 根据权利要求1所述的制备方法，其中，在步骤(3)中，相对于100mL第三溶剂，所述乙烯基磺酸盐的加量为0.05-0.5mol。
  14. 根据权利要求1或13所述的制备方法，其中，在步骤(3)中，所述乙烯基磺酸盐、所述乙烯基季铵盐与所述N-乙烯基吡咯烷酮的摩尔比为1：(1-3)：(0.5-1.5)，优选为1：(1.2-2.3)：(0.7-1.3)。
  15. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述氧化剂包括过硫酸铵和/或过硫酸钾。
  16. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述还原剂包括亚硫酸氢钠。
  17. 根据权利要求1所述的制备方法，其中，在步骤(3)中，相对于100mL第三溶剂，所述氧化剂的加量为0.001-0.005mol；
    优选地，在步骤(3)中，所述氧化剂和所述还原剂的摩尔比为1：(0.5-1.5)，更优选为1：(0.8-1.3)。
  18. 根据权利要求1所述的制备方法，其中，在步骤(3)中，所述第三接触反应的条件为：反应温度65-80℃，反应时间3-6h，且所述第三接触反应是在氮气气氛下进行的；优选地，所述第三接触反应在搅拌下进行，搅拌速度为600-800r/min。
  19. 一种微纳米级球形改性二氧化硅酸液胶凝剂，其是通过权利要求1-18中任一项所述的制备方法制备得到的；
    优选地，所述微纳米级球形改性二氧化硅酸液胶凝剂的平均粒径为500-2000nm，更优选为500-900nm；
    优选地，所述微纳米级球形改性二氧化硅酸液胶凝剂在质量分数为20％HCl水溶液中，在180℃、170s-1条件下剪切1h，其表观粘度大于45mPa·s。
  20. 权利要求19所述的微纳米级球形改性二氧化硅酸液胶凝剂在酸化压裂中的应用；
    优选地，所述酸化压裂的目标储层温度为150℃以上，更优选为180℃以上。
PCT/CN2023/096216 2022-07-08 2023-05-25 一种微纳米级球形改性二氧化硅酸液胶凝剂及其制备方法与应用 Ceased WO2024007759A1 (zh)

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